Alkoxylation of n-methyl-n-hydrocarbylamides



Int. Cl. B01k 1/00 US. Cl. 204-59 3 Claims ABSTRACT OF THE DISCLOSURE A process for the alkoxylation of N-methyl-N-hydrocarbylamides comprising electrolyzing a solution of a nitrate salt, an N-methyl-N-hydrocarbylamide and a lower aliphatic alcohol.

BACKGROUND OF THE INVENTION This invention pertains to a new method of alkoxylating N-methyl-N-hydrocarbylamides.

In co-pending application S.N. 468,981 of Ross et al., now Patent No. 3,411,997, there is described a process for forming the same compounds which result from the instant process. The process of said co-pending application is more involved. For example, in order to form an N-alkoxymethyl-N-hydrocarbylamide according to said co-pending application, it is necessary first to prepare an N-lower acyloxymethyl-N-hydrocarbylamide. The alkoxy derivative is then formed by contacting the acyloxy compound with a primary or secondary alcohol in the presence of a catalytic quantity of a strong mineral acid. The present invention eliminates the formation of the intermediate and directly forms the N-alkoxymethyl-N- hydrocarbylamide.

SUMMARY OF THE INVENTION This invention relates to method of preparing N-alkoxymethyl-N-hydrocarbylamides by electrolyzing an electrolyte comprising a solution of a nitrate salt, an N-methyl- N-hydrocarbylamide, and a lower aliphatic alcohol. The electrolysis results in the substitution of an alkoxy group for a hydrogen on the methyl group of said amide. The nitrate salt can be any organic or inorganic nitrate salt. The preferred nitrate salt is ammonium nitrate. The lower alcohol is a C -C alcohol. The hydrocarbyl group of the amide can be a C -C aliphatic or aromatic group. The preferred lower amides are N,N-dimethylformamide, N,N dimethylacetamide and N,N dimethylbenzamide. Thus, in a more limited sense, the invention relates to a method which comprises anodically electrolyzing a solution of ammonium nitrate in a mixture of a C -C aliphatic alcohol and a member of the group consisting of N,N dimethylformamide, N,N dimethylacetamide and N,N-dimethylbenzamide.

The N-alkoxymethyl-N-hydrocarbylamides formed by the present process will have the following general formula:

where R is a C -C alkyl or aryl group,

R is a C -C alkyl group, and

R is a C -C hydrocarbyl group. Examples of hydro carbyl groups are ethyl, propyl, phenyl, p-tolyl, cyclohexyl, cyclohexenyl, and cyclopentenyl.

States Patent O Patented Aug. 5, 1969 The present process results in N-alkoxymethyl-N-hydrocarbylamides directly by an electrochemical route, rather than via a chemical reaction involving the use of an intermediate. Moreover, the yields of the present process are significantly higher than the chemical method of said co-pending application. The compounds of the present process find utility as highly polar, aprotic, organic reaction media; electrolyte solvents; and as solvents for fiber spinning.

DESCRIPTION OF THE INVENTION a Example I.-Formation of N-n-butoxymethyl-N- methylformamide but was decreased to 1 ampere near the close of the electrolysis. Additional l-butanol (20 ml.) was added during the course of the electrolysis. The excess was removed with the water pump, and ether was added. The precipitated salt was filtered, and the ether was removed. The residue was fractionated at 0.04 mm. and yielded 74.6 g. of N-n-butoxymethyl-N-methylformamide, B.P. 6264, n 1.4365. The amount of dimethylformamide converted to product was 53%. The yield based on the charged passed was 81.6%. A sample redistilled for analysis had B.P. 61 (0.01 mm.) and n 1.4364.

The same product was obtained in only 74% yield by treating N-formyloxymethyl N methylformamide with l-butanol in the presence of a catalytic quantity of hydrochloric acid.

Using exactly the same procedure as Example I with ammonium nitrate, methanol, and dimethylformamide, yielded 52% of N-methoxymethyl-N-methylformamide. Likewise, employing ammonium nitrate, ethanol, and dimethylformamide, yielded 66.8% of N-methoxymethyl- N-methylformamide. Electrolysis of ammonium nitrate, 1butanol and dimethylacetamide yielded 77.75% of N-nbutoxymethyl-N-methylacetamide. As a final example, the electrolysis of ammonium nitrate, ethanol, and N,N- dimethylbenzamide yielded N ethoxymethyl-N-methylbenzamide.

Obviously, many modifications and variations of the present invention are possible in the light of the above teachings. It is, therefore, to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described.

What is claimed is:

1. A method of preparing N-alkoxymethyl-N-hydrocarbylamides of the following formula:

O CHaO Ra R1-N where:

R is a C -C alkyl or aryl group R is a C -C alkyl group, and

R is a C -C hydrocarbyl group,

by electrolyzing an electrolyte comprising a solution of a nitrate salt, an N-methyl-N-hydrocarbylamide and an aliphatic alcohol; the electrolysis resulting in the substitu- 3 4 tion of an alkoxy group for a hydrogen on the methyl References Cited group of said amide. P

2. The method of claim 1 wherein the nitrate is ammo- UNITED STATES ATENTS Ilium min-am 3,411,997 11/ 1968 Ross et a1 204-59 3. The method of claim 2 wherein the amide is a member selected from the group consisting of N,N-dimethyl- 5 PATRICK GARVIN Pnmary Exammer amide, N,N-dimethylacetamide and N,N-dimethy1benz- U S C1 XR amide. 204 72 UNITED STATES PATENT OFFICE 5 CERTIFICATE OF CORRECTION Patent No. 3,459,643 Dated Aggmt 5, 19Q9 Inventor) Sidney D. Ross, et a1 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, line 44, that portion of the compound reading "N-methoxymethy1" should read N-ethoxymethyl SIGNED AND SEALED APR 141970 (SEAL) Attest: Edward M.Flemher, It. ILLIAM E. SGHUYLER, JR. i officer missi er of Patent:- 

